Polyazo dyestuffs and process of making same



Patented Jan. 6, 1942 roLYAzo DYESTUFFS AND rnoonss MAKING SAME Walter Anderau, Basel, "Switzerland, assignor to Basel, Switzerland the firm Society of Chemical Industry in Basle,

No. 337,317; In Switzerland June 10, 1939 10 Claims.

It'has been found that valuable polyazo dye- F- 'stuffs may be obtained by coupling diazotized starting components with middle components,

further diazotization and coupling with further middle and/or end components if, as starting components, aminosalicylic'acids, as middle components, compounds of the general formula wherein R represents a benzene radical in which the substituents Y and OZ are placed in the para position to one another and the amino group stands in the ortho position tothe group ()Z, and wherein Z represents the radical of a low aliphatic fatty acid which is united to the O -atom by meansof a chain carbon atom, where- "in further Y represents an alkyl, an O-alkylor an O-aralkyl group, and finally, as end components, amino-naphthol sulfonic acids are chosen, which are united to a, 1:3:5-triazine radical by means of their nitrogen atoms in the form of an imino group, the'triazine radical containing at least once the radical of a paraaminoazo 'dyestuflf as a substituent.

The aminosalicylic acids which serve as starting components may have the amino group, for

example, in the para-position to, the hydroxyl group and, if desired, may possess other substituents in addition, such as alkyl groups or halogens. r In the compounds of the above mentioned general formula, the group Z may be, for example,

the radical of a fatty acid or of the functional derivatives thereof, such as esters or acid amides, so for instance the radical of acetic of propionic acid, Y may be a low molecular alkyl radical,

suchas the methyl radical, or an alkoxy group, ,such 1 as the methoxy or ethoxy group, or an aralkoxy group, such as thegroup CsI- I5CH2O-.

; 'The coupling of the diaz o'tized aminosalicylic acids with the middle components takes place according to generally known methods, for example, in a weakly acid medium.

Instead of uniting diazotized aminosalicylic vacids directly with the middle components of the structure above mentioned, it is also possible to insertanother of the middle components known gtojazorchemistry between the aminosalicylie acids by the usual methods.

and the middle components above named, orbe- "tween these middle components and the end components. 7 Such a known middle component might be, for example, 1-aminonaphthalene-6- or -7'-s'ulfonic acid.

The compounds which come into question for use as middle components and which have the general formula given above may be obtained Those compounds in which Y stands for an O-alkyl'or an O-aralkyl group may be advantageously prepared from nitrohydroquinone-alkyl or aralk'yl-ethers by treating these ethers with catalysts of the Friedel- Crafts type, such 'as aluminium chloride, when the ether group standing in the'ortho position to the nitro-group is saponified, the resulting nitro compound is reduced to the corresponding amine from which, for exampleby condensation with chloracetic acid chloride, by means of the intermediate stage of the morpholone, the 1-amino-5-alkoxyor -5-aralkoxy-2-phenoxyacetic acid may beobtained. v

As end components, such--naphthol sulfonic acids which are capable of coupling may be used in carrying out the present process, whose structure is characterized by the presence of the 1:3 5- triazine ring, which ring containsthe radical of a p-aminoazodyestuif at least once as a sublstituent. These compounds are obtained, for ex ample, by the condensation of cyanuric chloride with aminonaphthol sulfonic acids, aminoazo dyestuffs andother'products containing amino groups. vThe methodzof preparing this type of compound is described in detailin U. S. A. Patents 1,625,530, 1,625,531 and 1,625,532.

The method of preparation of compounds which contain a ternary substituted .1':3:-5-triazine ring depends on the property of cyanuric chloride, for example, to enter into reaction with amines which have an exchangeable hydrogen atom at the nitrogen atom, while splitting-off all 3 chlorine atoms, whereby in place of the chlorine atoms the substituents are united with the 1:3:5- triazine ring by means of their nitrogen atoms in the form of imino groups. Furthermore since the three chlorine atoms of the cyanuric chloride do not react with equal ease, the possibility exists of introducing different substituents by stages into the 1:3:5-triazine. ring in the manner mentioned -above. 'Thus, for instance, by stirring ll d-CHr-OOOH HO NH-C Finally, by heating under reflux with a further addition of sodium acetate, the third chlorine atom may be caused to enter into reaction with a third molecule of an amine in the same man- Particularly valuable products as regards nois in which, in the condensation with cyanuric chloride, in addition to ammonia or aromatic amines, sulfonic acids of 1 :8-aminonaphthol, such as 1-amino-8-hydroxynaphthalene-3 6-disulf onic acid, and p-aminoaz o compounds are used, which have been prepared from diazotized aminosalicylic acids by coupling with amines, for example, aniline.

The products obtained are suitable for dyeing and printing the most varying materials. They are particularly suitable for the dyeing of cellulosic fibres, such as cotton, linen, regenerated cellulose in the form of rayon or staple fibre, and similar textile fibres. The fastness properties of the dyeings obtained may be improved by arter treatment with agents yielding metals, particularly with copper salts, in the dyebath or in a fresh bath, inwhich case the dyeing process of U. S. A. Patents 2,148,659 and 2,185,905 may be used. It is especially possible to prepare very pure green dyeings of very good general fastness with the dyestuffs obtained by means of the present invention.

Inmany cases the dyestuffs obtained according to the present process may also be converted in substance into metal, particularly into copper and/or chromium compounds by known methods. Example 1 T mol of 4-amino-'1-hydroxybenzene-2-carboxylic acid is dissolved in 400 parts of water and 25 parts by volume of concentrated hydrochloric acid and is then diazotized by means of 7 parts of sodium nitrite at C. mol of the sodium salt of 5-methoxy-l-amino-Z-phenoxyacetic acid is then added. The excess of mineral acid is neutralized by addition of sodium acetate. Coupling is allowed to take place for 24 hours, after which the precipitate is filtered off.

The aminoazo dyestuff formed is dissolved in 400 parts of water at 50 C. and 25 parts by volume of caustic soda solution of strength, ice is added until the temperature has been lowered to 0 C. and then '7 parts of sodium nitrite are added. parts by'volume of concentrated hydrochloric acid are then added and the mixture isstirred for 1 hour. The diazo compound formed is added to the ternary condensation product obtained from mol of l-amino-8-hydroxynaphthalene-3:6-disulfonic acid and 1% mol of cyanuric chloride, mol of 4-amino-4'- hydroxy-B'-carboxyazobenzene and mol of aniline. Next, 60 parts of soda are added, whereupon coupling to a green dyestufi takes place. This is separated by addition of common salt and heating.

The dyestufi of the probable formula is a dark powder which dyes vegetable fibres in green shades. On aftertreatment with copper salts, the dyeings become purer and fast to light and washing.

Dyestuffs which yield similar green shades fast to light and washing when their dyeings on vegetable fibres are aftertreated with copper salts are obtained if the sodium salt of 5-methoxy-1- amino-2-phenoxyacetic acid be replaced by mol or G-methoxy --3 methyl-.l-aminobenzene or l-aminonaphthalene-G- or -7-sulfonic acid as first middle component, and, after further diazotization, 6 mol of the sodium salt of 5-phenyl-methoxy-l-amino 2 phenoxyacetic acid be used, or if solutions of the ternary condensation product obtained from mol of cyanuric chloride and {6 mol of aniline, mol of 4-amino- 4-hydroxy-3'-carboxyazobenzene and mol .Of 1-.arninoe8-hydroxynaphthalene 4:6 .disulfonic acid or -2Z.4-,.di$lllf0l1i0 acid ,or solutions of the ternary condensation product obtained from 1 mol of cyanuric chloride with mol of ammonia, mol of lwaminol'-hydroxy-3'-carboxyazobenzene and .mol of 1-:amino-8-hy- ,droxynaphthalene-4-sulfonic acid be used as end o flne fif tslmpl 2 15.3 parts of 4-amino-1-hydroxybenzene-2- carboxylic acid aredissolved in .25 parts by volume of concentrated hydrochloric acid and 200 parts of water and are diazotized with 7 parts of sodium nitrite. At 0 the resulting diazo solution is freed from excess of mineral acid by addition of sodium acetate, and then a solution of 23.5 parts of the sodium salt of 5-ethoxy-1- amino- 2-phenoxyacetic acid in 300 parts of water is added. After some hours, the aminoazo compound has been formed as a violet precipitate. This is separated by filtering and redissolved in 400 parts of water and 25 parts of caustic soda solution of 40 B. The solution is coo1ed'to0 C. with ice and '7 parts of sodium nitrite are added. The diazp compound is obtained as a brown suspension by adding 45 parts of concentrated hydrochloric acid to the cooled solution. This is "now allowed to run into a solution of the ternary condensation product obtained from 18 parts of cyanuric chloride, 34.1 parts of l-amino-8-hydroxynaphthalene-3:6-disulfonic acid, 257 parts of -amino-l hydroxy- '3'-carboxyazobenzene and 9.5 parts of aniline which has been made strongly alkaline with sodium carbonate. A green solution is formed from which'the dyestuff is precipitated 'by;a d'- 'dition of common saltto thewarm solution.

When dried, the dyestuif, which is probable'of the formula g forms a black powder which dissolves in water and dilute soda solution to a blue-green solution and which gives a green solution in dilute caustic soda and concentrated sulfuric acid. 20

When it is dyed on cotton or regenerated cellulose rayon from a Glaubers salt bath, bluegreen shades are obtained which become green on after treating with copper salts and are then 'fast to light and washing. v

5 taining in the remaining place a radical selected Dyestuffs which yield similar green shades fast to light and washing'when their dyeings on vegetable fibres are aftertreated with copper salts are obtained if the 15.3 parts of 4-amino- 1-hydroxybenzene-2-carboxylic acid be replaced as starting components by 16.7 parts of 6-methyl- 4l-amino-1-hydroxy-benzene-2-carboxylic acid, of 18.9 parts of 6-chloro-4-amino-lv-hydroxybenzen'e-2-carboxy1ic acid, or if in place of 23.5 parts of the sodium salt of l-amino--ethoxy-zphenoxyacetic acid as middle component 20.5 parts of the sodium salt of 1-amino-5-methyl-2-phenoxyacetic acid be used, or if, as end component,

a solution of the ternary condensation product parts of 1-amino-8-hydroxy-naphthalene-3:6- disulfomc acid, 27.1 parts of 4-amino-5'-methyl- 4'-hydroXy-3'-carboxyazobenzene and 9.5 parts of aniline or a solution of the ternary condensation product obtained from 18 parts ofcyanuric chloride, 34.1 parts ofI-ainino-S-hydroxy-naphthalene-3z6-disulfonic acid, 29.2 parts of 4- amino-5'-chloro- 4'-hydroxy 3'-carboxyazobenzene and 9.5 parts of aniline be used. v

Example 3 A dyebath is prepared containing 2500 parts of water, 2 parts of the dyestuif obtained in Example 1 and 2 parts of anhydrous sodium carbonate. 100 parts of cotton, which have already been wetted-out, are entered into this bath at 50 C.,

and the temperature is raised in '15 minutes to 80-90 C.,' whereupon 30" parts of crystalline,

sodium sulfate are added, and dyeing is 'continued at about 90 C. for a further hour.

The cotton is then rinsed and is after-'coppered Q The cotton is dyed a fast shade of green.

What I claim is:

1. Process for the manufacture of polyazo dyestuffs, comprising coupling a diazotized aminoazo-dyestufi having as starting component a para-aminosalicylic acid and as middle component a compound of the general formula NHi noocQ v a A v H I l p v represents the radical of a low aliphatic fatty acidwhich is united to the O-atom by means of a, chain carbon atom, wherein further Y represents a member of the group consisting of alkyl, .O-alkyl and O-aralyl groups, with an aminonaphthol sulfonic acid linked to a 1:3:5-triazine radical by means of its nitrogen atom, thesaid triazine radical being further linked to at least one radical of a para-aminoazo dyestufi and connoazo-dyestuif having as starting component a para-aminosalicylic acid and as middle component'a compound of the general formula v I oz wherein R- represents a benzene radical in which p the substituents Y and OZ are placed in para.- obtained from 18 parts-of cyanuric chloride, 34.1 o

" naphthol sulfonic acid linked to a 1:3:5-triazine radical by means of its nitrogen atom, the said triazine radical being further linkedto at least one. radical of a para-aminoazoedyestuif containing a para-amino-salicylic acid as 'iirst com ponent, said triazine radical containing in the remaining place a radical of an aromatic amine linked by means of its nitrogen atom.

3. Processfor the manufacture of polyazo dyestuffs, comprising coupling a diazotized aminoazodyestuff having as starting component a para-aminosalicylic acid and as middle component acompound of the general formula wherein Rrepresents a benzene radical in which the substituents Y and OZ are placed in paraposition to one another and the amino group stands in ortho-position to'OZ, and wherein Z represents the group CH2COOH, wherein further Y represents a member of the group consisting of alkyl, O-alkyl and O-aralkyl groups, with an aminonaphthol sulfonic acid linked to a 1:3:5-triazine radical by means of its nitrogen atom, the said triazine radical being further linked to at least one radical of a para-aminoazo-dyestufi containing a para-aminosalicylic acid as first component, said triazine radical contain n in the rem ini g p c a v a ic o an ar t c mine link d by m a of s n trog n atom. I I

4. Process for the manufacture of polyazo dyestuffs, comprising coupling a diazotized aminoazo-dyestufi obtained from diazotized 4-aminol-hydroxybenzene-2-carboxylic acid methoxy-l-amino-Z-phenoxyacetic acid with the ternary condensation product from 1 mol cyanuric chloride and 1 ,mol each of 1-amino-8- hydroxynaphthalene 3:6 4 disulfonic acid, 4- amino 4' hydrox'y 3'-carboxyazobenzene and aniline.

5. Process for the manufacture of polyazo dyestuffs, comprising coupling a diazotized aminoazo-dyestuff obtained from dia-zotized 4-aminoe1- hydroxybenzene-Z-carboxylic acid and 5-ethoxyl-amino-Z-phenoxyacetic acid with the ternary condensation product from 1 mol cyanuric chloride and 1 mol each of 1-amino-8-hydroxynaphthalene 3:6- disulfonic acid, 4-amino-4'-hydroxy-B'-carboxyazobenzene and aniline.

6. Pol'yazo dyestuffs of the general formula it Y wherein R represents the radical of a salicylic acid in which the O H-group stands in para position to the azo group, Y a member of the group consisting of an alkyl, an O'-alky1 and an O- aralkyl group, Z the radical of a low aliphatic fatty acid which is united to the O-atom by means of a chain carbon atom, and R2 the radical of an aminonaphthol sulfonic acid which is unitand 5- y ed to a 1:3:5-triazine radical by means of its I 00011 $0113 HQaS I 00011 6-CaHs radical of a para-aminoazo dyestuff as a substituent.

7. Polyazo dyestufis of the general formula SOaH 1 is the radical of a para-aminoazo dyestuff built up from a para-aminosalicylic acid and the remaining is an aromatic amine radical, are united by means of their nitrogen atoms in the form of imino groups.

8. Pelyazo dyestuffs ofthe general formula wherein, R1 represents the radical of a salicylic acid in which the O'H-gr0up stands in paraposition to the azo-group, Y is a member of the group consisting of an alkyl, an o-alkyl and an O- ar lkyl r up, Z Stands for the up wherein further Rzstands for the radical of a naphthol sulfonic acid, and finally R3 stands for the radical of a ternary substituted 1 :315-triazine with. which also the other two substituents, of

which at least one is the radical of a para-aminoazodye-stufi built up from a para-aminosalicylic acid and the remaining is an aniline radical, are united by means of their nitrogen atoms in the .fo .o 1 mm s ups- 9. The trisazo dyestufi of the formula 1713:106 N N l H v 370 ,l- Hr N; OH

N l t r HOOC SOaH 10. The trisazo dyestufi of the formula WALTER ANDERAU.

. cmmmcam or CORRECTION. Patent Nq. 2,268,919. January 6, 191m.

WALTER ANDERAU It is hereby'certified thafi error appears in the .above .numbezoefi patent requiring correction as follows: In the heading to th printed specification; line 7, for "No. 557,317 read App11 :gt1on Hay 25, 1594.0, Serial No.'. 357,511; and that the said Letters Patent should be read wijzh this corrction'fherein th'atfihe same may conform to the record of the case in the Patent Office. j

Signed and sealed this 20th day of April, A. D.-14.5.

He nry Van Arsdale (Seal) Acting commissioner pf Patents. 

